Photoimageable compositions and processes for fabrication of relief patterns on low surface energy substrates

Abstract

The present invention is directed to a permanent photoimageable compositions and the cured products thereof useful for making negative-tone, permanent photoresist relief patterns on low surface energy polymer substrates, comprising: (A) one or more alkali soluble, film forming resins or one or more film forming resins that become soluble in alkali solutions by action of an acid, (B) one or more cationic photoinitiators, (C) one or more film casting solvents, and (D) one or more fluorinated compounds. The present invention is also directed to methods of forming a permanent photoresist relief pattern on a low surface energy polymer substrate using the disclosed compositions.

What is claimed is: 
     
       1. A permanent photoimageable composition useful for making permanent photoresist relief patterns on low surface energy polymer substrates comprising:
 (i) one or more alkali soluble, film-forming resins (A) or one or more film forming resins that become soluble in alkali solutions by action of an acid (B); wherein the one or more alkali soluble film forming resins (A) are selected from the group consisting of phenol novolac resins, ortho-cresol novolac resins, para-cresol novolac resins, ortho, para-novolac resins, bisphenol novolac resins, polyhydroxy novolac resins, polyglutarimide resins, phenolic derivatives of C36 dimerdiols, polyester resins synthesized from polyhydric alcohols and polybasic acid compounds, the reaction products of epoxy resins, monocarboxylic acids, and polybasic acid anhydrides, and combinations thereof; 
 (ii) a cationic photoinitiator (C), and a radical photoinitiator (D);
 wherein said radical photoinitiator (D) is selected from the group consisting of benzoin ethers, benzoin methyl ethers, diethoxyacetophenone, benzildimethyl ketal, hexaarylbisimidazole, 2-tertbutylanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, oxime esters, ketocoumarin derivatives, organotitanocenes, and combinations thereof; and wherein the radical photoinitiator (D) comprises from 0.1-10 wt %, based on the total weight of the composition; 
 
 (iii) one or more film casting solvents (E); and 
 (iv) one or more fluorinated compounds (F);
 wherein said fluorinated compound is selected from the group consisting of perfluorohexane, perfluorooctane, perfluorodecalin, 2,3-dihydrofluoropentane, hexafluorobenzene, 1,1,2,2,3,3,4,4-octafluorobutane, perfluorodimethylcyclohexane, perfluoroheptane, perfluoromethylcyclohexane, perfluoropentane, 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)-hexane furan, 2,2,3,4,4,5-hexafluorotetrahydro-3-(pentafluoroethyl)-5-(trifluoromethyl)-cis-furan, 2,2,3,4,4,5-hexafluorotetrahydro-3-(pentafluoroethyl)-5-(trifluoromethyl)-, trans-furan, 2,2,3,4,4,5-hexafluorotetrahydro-5-(pentafluoroethyl)-3-(trifluoromethyl)-trans-furan, 2,2,3,4,4,5-hexafluorotetrahydro-5-(pentafluoroethyl)-3-(trifluoromethyl)-cis-furan, 2,3,3,4,4,5-hexafluorotetrahydro-2-(pentafluoroethyl)-5-(trifluoromethyl)-, 2h-cyclopenta[b]furan, 2,2,3,3a,4,4,5,5,6,6,6a-undecafluorohexahydro-3-(trifluoromethyl)-furan, 2,2,3,4,4,5-hexafluorotetrahydro-3,5-bis(pentafluoroethyl)-furan, 2,2,3,4,4,5-hexafluoro-3-(heptafluoropropyl)tetrahydro-5-(trifluoromethyl)-furan, 2,2,3,4,4,5-hexafluoro-5-(heptafluoropropyl)tetrahydro-3-(trifluoromethyl)-trans-furan, 2,2,3,4,4,5-hexafluoro-5-(heptafluoropropyl)tetrahydro-3-(trifluoromethyl)-cis-furan, 2,3,3,4,4,5-hexafluoro-2-(heptafluoropropyl)tetrahydro-5-(trifluoromethyl)-, 1,1,1,2,2,3,3,4,4-nonafluorohexane, perfluoromethylcyclopentane, dodecafluorodimethylcyclobutane, lh,lh,2h-perfluoro-1-decene, perfluoro-1,3-dimethylcyclohexane, lh-perfluoroheptane, perfluoroheptene-1,6h-perfluorohexane, perfluoromethyldecalin, perfluorooctene-1, lh,lh,2h-perfluoro-1-octene, perfluorononane, perfluorodecane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-methoxy-hexane, 2-difluoromethylperfluorooxolane, perfluorotri-n-butylamine/perfluoro-n-dibutylmethylamine mixture; perfluorotributylamine, perfluoro-N-alkylmorpholine, and combinations thereof; and one or more crosslinking compounds. 
 
 
     
     
       2. The permanent photoimageable composition of  claim 1 , wherein the one or more film forming resins that become soluble in alkali solutions by action of an acid are selected from the group consisting of poly(hydroxystyrenes), derivatized copolymers of hydroxystyrene and acrylic monomers, derivatized copolymers and terpolymers of hydroxystyrene, styrene, and acrylic monomers, polymeric resins containing alkyl and alicyclic repeating units, and derivatized copolymers and terpolymers of acrylic monomers, and combinations thereof. 
     
     
       3. The permanent photoimageable composition of  claim 1 , wherein the cationic photoinitiator is selected from the group consisting of di-(t-butylphenyl)iodonium triflate, diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, [4-(octyloxy)phenyl]phenyliodonium hexafluoroantimonate, triphenylsulfonium triflate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4′-bis[diphenylsulfonium[diphenylsulfide bis-hexafluorophosphate, 4,4′-bis[di((3-hydroxyethoxy)phenylsulfonium[diphenylsulfide bis-hexafluoroantimonate, 4,4′-bis[di((3-hydroxyethoxy)(phenylsulfonium)diphenyl sulfide-bishexafluorophosphate 7-[di(p-tolyl)sulfonium[-2-isopropylthioxanthone hexafluorophosphate, 7-[di(p-tolyl)sulfonio-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-tolyl)sulfonium[-2-isopropyl tetrakis(pentafluorophenyl)borate, phenylcarbonyl-4′-diphenylsulfonium diphenylsulfide hexafluorophosphate, phenylcarbonyl-4′-diphenylsulfonium diphenylsulfide hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4′-diphenylsulfonium diphenylsulfide hexafluorophosphate, 4-tert-butylphenylcarbonyl-4′-diphenylsulfonium diphenylsulfide hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4′-diphenylsulfonium diphenylsulfide tetrakis(pentafluorophenyl)borate, diphenyl [4-(phenylthio)phenyl[sulfonium hexafluoroantimonate, mixed aromatic sulfonium hexafluoroantimonate salts, tris(4-(4-acetylphenylthio)phenyl)sulfonium tetrakis(pentafluorophenyl)borate, tris(trifluoromethanesulfonyl(methide), benzoin tosylate, t-butylphenyl alpha-(p-toluenesulfonyloxy)-acetate and t-butyl alpha-(p-toluenesulfonyloxy)-acetate, nitrobenzyl esters, s-triazine derivatives 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane (DDT); 1,1-bis[p-methoxyphenyl]-2,2,2-trichloroethane; 1,2,5,6,9, 1 0-hexabromocyclodecane;1,1 0-dibromodecane; 1,1-bis[p-chlorophenyl]-2,2-dichloroethane; 4,4-dichloro-2-(trichloromethyl)benzhydrol (Kelthane): hexachlorodimethyl sulfone; 2-chloro-6-(trichloromethyl)pyridine; o,o-diethyl-o-(3,5,6-trichloro-2-pyridyl) phosphorothionate;1,2,3,4,5,6-hexachlorocyclohexane; N-(1,1-bi s [p-chlorophenyl]-2,2,2-trichloroethyl)acetamide, tris [2,3-dibromopropyl] isocyanurate; 2,2-bis [p-chlorophenyl] 1,1-dichloroethylene; tris[trichloromethyl]-s-triazine; and their isomers, analogs, homologs, and combinations thereof. 
     
     
       4. The permanent photoimageable composition of  claim 1 , wherein the film casting solvents are selected from the group consisting of acetone, 2-butanone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, methyl t-butyl ketone, cyclopentanone, cyclohexanone, dipropylene glycol dimethyl ether, tetrahydrofuran, tetrahydrofurfuryl alcohol 1,3-dioxolane, 1,4-dioxane, dimethoxyethane, diglyme, ethyl acetate, butyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, gamma-butyrolactone, dimethyl carbonate, diethyl carbonate, propylene carbonate toluene, xylene, 1,2,4,5-tetramethylbenzene, octane, decane, petroleum distillates, and combinations thereof. 
     
     
       5. The permanent photoimageable composition of  claim 1 , wherein said crosslinking compounds are selected from the group consisting of diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolpropane triglycidyl ether, propylene glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, bisphenol A, bisphenol F, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3′,5,5′-tetramethyl-[1,1′-biphenyl]-4,4′-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, and 1,1,2,2,-tetrakis(4-hydroxyphenyl)ethane, xylylene dioxetane, bis(3-ethyl-3-oxetanylmethyl)ether, alkoxymethylmelamines, alkoxyamethylglycolurils, alkoxymethylbenzoguanamines, alkoxymethyldiguanamines, melamine or benzoguanamine polymers, 1,6-hexandiol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylates having 2 to 20 of repeating units, pentaerythritol diacrylate, dipentaerythritol hexacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, methylene bisacrylamide, N-methylolacrylamide, and combinations thereof. 
     
     
       6. The permanent photoimageable composition of  claim 5 , wherein the crosslinking compound comprises from 1-30 wt %, based on the total weight of the composition. 
     
     
       7. The permanent photoimageable composition of  claim 1 , further comprising one or more surfactants selected from the group consisting of fluorinated poly(oxetane) polymers, fluorosurfactants and combinations thereof. 
     
     
       8. The permanent photoimageable composition of  claim 7 , wherein the surfactant comprises from 0.001-5 wt %, based on the total weight of the composition. 
     
     
       9. The permanent photoimageable composition of  claim 1 , further comprising one or more epoxy resins selected from the group consisting of epoxy cresol-novolac resin with an epoxide equivalent weight of about 195 g/eq. 
     
     
       10. The permanent photoimageable composition of  claim 9 , wherein the epoxy resin comprises from 5-40 wt %, based on the total weight of the composition. 
     
     
       11. The permanent photoimageable composition of  claim 1 , further comprising one or more photosensitizer compounds selected from the group consisting of anthracene derivatives, N-alkyl carbazole derivatives, halo-fluorone derivatives, 9,10-dialkoxyanthracenes, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dimethoxy-2-ethylanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-dipropoxy-2-ethylanthracene, 9,10-dimethoxy-2-chloroanthracene, 9,10-dimethoxyanthracene-2-sulfonic acid, 9,10-dimethoxyanthracene-2-sulfonic acid methyl ester, 9,10-diethoxyanthracene-2-sulfonic acid methyl ester, 9,10-dimethoxyanthracene 2-carboxylic acid, 9,10-dimethoxyanthracene-2-carboxylic acid methyl ester, N-ethyl carbazole, N-ethyl-3-formyl-carbazole, 1,4,5,8,9-pentamethyl-carbazole, N-ethyl-3,6-dibenzoyl-9-ethylcarbazole and 9,9′-diethyl-3,3′-bicarbazole, 5,7-diiodo-3-butoxy-6-fluorone, 3-hydroxy-2,4,5,7-tetraiodo-6-fluorone, and 9-cyano-3-hydroxy-2,3,5,7-tetraiodo-6-fluorone, coumarin derivatives, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl 1-5-mercapto-1H-tetrazole, 2-mercapto-4-phenylthiazole, 2-amino-5-mercapto-4-phenylthiazole, 2-amino-4-mercapta-1,3,4-thiazole, 2-mercaptoimidazole, 2-mercapto-5-methyl-1,3,4-thiazole, 5-mercapto-1-methyl-1H-tetrazole, 2,4,6-trimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2,5-dimercapto-1,3,4-thiadiazole,5-mercapto-1,3,4-thiadiazole, 1-ethyl-5-mercapto-1,2,3,4-tetrazole, 2-mercapto-6-nitrothiazole, 2-mercapto-benzoxazole, 4— phenyl-1-2-mercaptothiazole, mercaptopyridine, 2-mercaptoquinoline, 1-methyl-2-mercaptoimidazole, 2-mercapto-(naphthothiazole), and combinations thereof. 
     
     
       12. The permanent photoimageable composition of  claim 11 , wherein the photosensitizer comprises from 0.05-4 wt %, based on the total weight of the composition. 
     
     
       13. The permanent photoimageable composition of  claim 1 , further comprising one or more adhesion promotors selected from the group consisting of 3-glycidoxypropyltrimethoxy silane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltriethyoxysilane, and combinations thereof. 
     
     
       14. The permanent photoimageable composition of  claim 13 , wherein the adhesion promotor comprises from 0.1-3 wt %, based on the total weight of the composition. 
     
     
       15. The permanent photoimageable composition of  claim 1 , further comprising one or more light-absorbing compounds selected from the group consisting of 2,4-dihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, phenyl salicylate, 4-t-butylphenyl salicylate, ethyl-2-cyano-3,3-diphenylacrylate, 2′-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2,4-dihydroxyazobenzene, 4-methyl-7-diethylamino-1-benzopyran-2-one, diethylthioxanthone, 1-chloro-4-propoxy-thioxanthone, thioxanthone compounds, stilbene compounds, naphthalic acid compounds, and combinations thereof. 
     
     
       16. The permanent photoimageable composition of  claim 15 , wherein the light-absorbing compound comprises from 0.25-50 wt %, based on the total weight of the composition. 
     
     
       17. The permanent photoimageable composition of  claim 1 , further comprising one or more light-absorbing compounds having the general structure C+D − , where C + is the cationic species and D − is the anionic species. 
     
     
       18. The permanent photoimageable composition of  claim 17 , wherein the cationic species is selected from the group consisting of cyanine cation, aminoanthroquinone cation, azine cation, rhodamine cation, fuchsin cation, xanthene cation, and combinations thereof. 
     
     
       19. The permanent photoimageable composition of  claim 17 , wherein the anionic species is selected from the group consisting of SbF 6   − , BF 4   − , PF 6   − , AsF 6   − , (CF 3 SO 2 ) 3 C − , (CF 3 CF 2 ) 3 PF 3   − , (C 6 F 5 ) 4 B − , and combinations thereof. 
     
     
       20. The permanent photoimageable composition of  claim 1 , further comprising one or more flexibilizing compounds selected from the group consisting of caprolactone polyols, dimethyl adipate, dihexyl adipate, dioctyl phthalate and combinations thereof. 
     
     
       21. The permanent photoimageable composition of  claim 20 , wherein the flexibilizing compound comprises from 1-70 wt %, based on the total weight of the composition. 
     
     
       22. The permanent photoimageable composition of  claim 1 , further comprising a quencher selected from the group consisting of n-boc-piperidine, t-butyl-4-hydroxy-1-piperidinecarboxylate, triethanol amine, 1-piperidineethanol, benzyltriethylammonium chloride, and combinations thereof. 
     
     
       23. The permanent photoimageable composition of  claim 22 , wherein the molar ratio of quencher to photoacid generator is from 0.2 to 10. 
     
     
       24. The permanent photoimageable composition of  claim 1 , wherein the one or more alkali soluble, film-forming resins (A) comprises from 5-90 wt %, based on the total weight of the composition. 
     
     
       25. The permanent photoimageable composition of  claim 1 , wherein the cationic photoinitiator (C) comprises from 0.1-10 wt %, based on the total weight of the composition. 
     
     
       26. The permanent photoimageable composition of  claim 1 , wherein the film casting solvent comprises from 5-99 wt %, based on the total weight of the composition. 
     
     
       27. The permanent photoimageable composition of  claim 1 , wherein the fluorinated compound comprises from 0.01-10 wt %, based on the total weight of the composition. 
     
     
       28. The composition of  claim 1 , further comprising one or more additional materials including, without limitation, flow control agents, thermoplastic and thermosetting organic polymers and resins, inorganic filler materials, and radical photoinitiators.